CN105051111A - Resin composition and adhesive film, coverlay film, and interlayer adhesive using resin composition - Google Patents

Resin composition and adhesive film, coverlay film, and interlayer adhesive using resin composition Download PDF

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Publication number
CN105051111A
CN105051111A CN201480015746.8A CN201480015746A CN105051111A CN 105051111 A CN105051111 A CN 105051111A CN 201480015746 A CN201480015746 A CN 201480015746A CN 105051111 A CN105051111 A CN 105051111A
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composition
halogen atom
resin combination
alkyl
carbon number
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CN201480015746.8A
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CN105051111B (en
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寺木慎
日马宗俊
吉田真树
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Namics Corp
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Namics Corp
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/281—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polyimides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J153/00—Adhesives based on block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J153/02—Vinyl aromatic monomers and conjugated dienes
    • C09J153/025—Vinyl aromatic monomers and conjugated dienes modified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/732—Dimensional properties
    • B32B2307/734—Dimensional stability
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2457/00—Electrical equipment
    • B32B2457/08—PCBs, i.e. printed circuit boards
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/14—Peroxides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
    • C08K5/3415—Five-membered rings
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/22—Secondary treatment of printed circuits
    • H05K3/28—Applying non-metallic protective coatings
    • H05K3/281—Applying non-metallic protective coatings by means of a preformed insulating foil
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/46—Manufacturing multilayer circuits
    • H05K3/4644—Manufacturing multilayer circuits by building the multilayer layer by layer, i.e. build-up multilayer circuits
    • H05K3/4673—Application methods or materials of intermediate insulating layers not specially adapted to any one of the previous methods of adding a circuit layer

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Non-Metallic Protective Coatings For Printed Circuits (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Production Of Multi-Layered Print Wiring Board (AREA)

Abstract

Provided are: a resin composition that can be thermally cured at 180 DEG C or lower, the resin composition having excellent adhesive strength to substrate materials, electrical properties in the high-frequency region of a frequency of 1 GHz or higher, specifically, a low dielectric constant (epsilon) and a low dielectric loss tangent (tan delta) in the region of a frequency of 1 GHz or higher, as well as little shrinkage stress during thermal curing; and an adhesive film and a coverlay film produced using this resin composition. This resin composition includes (A) a vinyl compound indicated by general formula (1), (B) a polystyrene-poly(ethylene/butylene) block copolymer having a styrene content of 25-40%, (D) an epoxy resin, (E) bismaleimide, and (F) an organic peroxide having an exothermic peak measured by differential scanning calorimetry (DSC) of 100-180 DEG C, the mass ratio of each component being (A + E)/(B + C) = 0.81-1.00, (B)/(C) = 1.00-4.00, and the resin composition containing 1-10 mass% of component (D) by mass percent in relation to the total mass of components (A)-(F) and 0.1-10 mass% of component (F) by mass percent in relation to the content of component (A).

Description

Resin combination and the adhesive film adopting it to obtain, mulch film, layers cementing agent
Technical field
The present invention relates to resin combination.More specifically, a kind of resin combination being suitable for the adhesive film of electrical/electronic purposes or the mulch film of printed circuit board (PCB) is related to.
In addition, the present invention relates to the adhesive film using this resin combination to make and mulch film.
In addition, the invention still further relates to the application of this resin combination in the layers cementing of multilayer printed circuit.
Background technology
In recent years, the printed circuit board (PCB) used in electric/electronic, the miniaturization of its machine, lightweight and high performance, in progress, especially for multilayer printed circuit board, require further high multiple stratification, densification, slimming, lightweight, high reliability and shaping processability etc.
In addition, along with the high speed requirement of the recent transmission signal to printed circuit board (PCB), the high frequency of transmission signal is carried out significantly.Thus, for the material that printed circuit board (PCB) uses, requirement can be reduced in the electrical signal loss in the region of high-frequency region, specifically more than frequency 1GHz.
For the layers cementing agent used in multilayer printed circuit board, the adhesive film that uses as the surface protection film (i.e. mulch film) of printed circuit board (PCB), also require in the excellent electrical characteristic (low-k (ε), low dielectric loss angle tangent (tan δ)) of high-frequency region display.
Patent Document 1 discloses and can obtain low-k, low dielectric loss angle tangent and the cured article of thermotolerance, mechanical characteristics, chemical-resistant, excellent in flame retardance and can at the curable resin composition of low-temperature curing and the solidified nature film employing this curable resin composition and the cured article, the film that make these curable resin compositions solidify.
On the other hand, propose in patent documentation 2 and to the tinsel of the wiring becoming flexible printed circuit board and the baseplate material of this flexible printed circuit board, there is excellent bonding strength and be presented at the electrical characteristic of the high-frequency region of more than frequency 1GHz, specifically at the mulch film of the region of more than frequency 1GHz display low-k (ε) and low dielectric loss angle tangent (tan δ).
Prior art document
Patent documentation 1: Japanese Unexamined Patent Publication 2009-161725 publication
Patent documentation 2: Japanese Unexamined Patent Publication 2011-68713 publication
Summary of the invention
When the layers cementing of multilayer printed circuit board, can because of string stress during thermofixation in layers cementing portion residual stress.If the stress deformation in layers cementing portion becomes large, then produce warpage and reliability reduction that through hole is connected.
In addition, in the adhesive film that the mulch film as flexible printed circuit board (FPC) uses, also warpage can be produced because of string stress during thermofixation.If produce this kind of warpage, then cause the flexibility of the FPC that originally should require impaired, such as, be difficult to be used as FPC cable.Be explained, this kind of warpage also forms problem when the mulch film of the rigid substrates aggravated as thin plateization uses.
In addition, during the thermofixation of the adhesive film used when the layers cementing of multilayer printed circuit board or as the mulch film of FPC, due to the appointed condition usually used in Substrate manufacture can be applied; If cool from the high temperature of more than 200 DEG C, then warpage when cooling becomes large, based on these reasons, it is desirable to the thermofixation implemented at lower temperatures.Specifically, it is desirable to implement thermofixation below 180 DEG C.
The object of the invention is to: in order to solve the problem points of above-mentioned prior art and the adhesive film providing a kind of resin combination and use this resin combination to make and mulch film, described resin combination is to epoxy resin, resol, the organic material substrates such as bismaleimide-triazine resin, person's ceramic substrate, the inorganic substrate material such as silicon substrate, and the baseplate material of the FPC such as polyimide film has excellent bonding strength, and except being presented at the electrical characteristic of high-frequency region of more than frequency 1GHz, specifically in the region of more than frequency 1GHz display low-k (ε), and beyond low dielectric loss angle tangent (tan δ), string stress during thermofixation is few, can thermofixation below 180 DEG C.
To achieve these goals, the invention provides a kind of resin combination, it comprises:
(A) the matter average molecular weight (Mw) shown in following general formula (1) is the vinyl compound of 500 ~ 4000;
(in formula, R 1, R 2, R 3, R 4, R 5, R 6and R 7can be hydrogen atom, halogen atom, alkyl, haloalkyl or phenyl identical or differently.-(O-X-O)-represent with following structural formula (2).
R 8, R 9, R 10, R 14and R 15can be halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently.R 11, R 12and R 13can be hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently.-(Y-O)-be the a kind of structure defined with following structural formula (3) or the structure become through random arrangement with the structure of more than two kinds that following structural formula (3) defines.
R 16and R 17can be halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently.R 18and R 19can be hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently.Z is the organic radical of carbon number more than 1 and sometimes also comprises Sauerstoffatom, nitrogen-atoms, sulphur atom, halogen atom.A and b represents the integer of 0 ~ 300 and at least any one party is not 0.C and d represents the integer of 0 or 1.)
(B) styrene content is polystyrene-poly (ethylene/butylene) segmented copolymer of 15 ~ 35%;
(C) styrene content is polystyrene-poly (ethylene-vinyl/propylene) segmented copolymer of 25 ~ 40%;
(D) epoxy resin;
(E) bismaleimides; And
(F) exothermic peak utilizing means of differential scanning calorimetry (DSC) to measure to obtain more than 100 DEG C and the organo-peroxide of less than 180 DEG C,
The mass ratio of each composition be (A+E)/(B+C)=more than 0.81 and less than 1.00, (B)/(C)=more than 1.00 and less than 4.00,
With the mass percent of the total mass relative to mentioned component (A) ~ (F), the mentioned component (D) containing 1 ~ 10 quality %,
With the mass percent of the content relative to above-mentioned (A) composition, the mentioned component (F) containing 0.1 ~ 10 quality %.
In resin combination of the present invention, preferred: mentioned component (A)-(O-X-O)-represent with following structural formula (4), mentioned component (A)-structure that becomes through random arrangement of (Y-O)-have following structural formula (5) or the structure shown in following structural formula (6) or the structure shown in following structural formula (5) and the structure shown in following structural formula (6).
In resin combination of the present invention, preferably: the organo-peroxide of above-mentioned (F) composition is peroxyesters or dialkyl peroxide class.
In resin combination of the present invention, preferably: the epoxy resin of above-mentioned (D) composition be selected from there is not hydroxyl in the molecule biphenyl type epoxy resin, fluorenes type epoxy resin and naphthalene type epoxy resin at least a kind.
In addition, the invention provides the adhesive film comprising resin combination of the present invention.
In addition, the invention provides the multilayer printed circuit board employing resin combination of the present invention or adhesive film of the present invention in layers cementing.
In addition, preferred: the substrate forming multilayer printed circuit board of the present invention for the vinyl compound shown in above-mentioned general formula (1) and, rubber and/or thermoplastic elastomer be the resin substrate of principal constituent.
In addition, the invention provides the mulch film comprising resin combination of the present invention.
In addition, the invention provides the flexible printed circuit board with mulch film of the present invention.
In addition, the invention provides a kind of flexible printed circuit board, it is characterized in that, in the wiring pattern side of resin substrate wiring pattern being formed at the band wiring obtained with the interarea of the resin substrate that is principal constituent of any one in liquid crystalline polymers, polyimide and PEN, use mulch film of the present invention.
In addition, the invention provides a kind of flexible printed circuit board, it is characterized in that, in the wiring pattern side of resin substrate wiring pattern being formed at the band wiring obtained with the vinyl compound shown in above-mentioned general formula (1) and rubber and/or the thermoplastic elastomer interarea that is the resin substrate of principal constituent, use mulch film of the present invention.
Invention effect
Resin combination of the present invention, to the baseplate material becoming the FPC such as the tinsel of wiring of FPC or polyimide film, there is excellent bonding strength, and show excellent electrical characteristic at high-frequency region, specifically at the region of more than frequency 1GHz display low-k (ε) and low dielectric loss angle tangent (tan δ), be therefore suitable as the mulch film of FPC.
In addition, resin combination of the present invention also has excellent bonding strength to the organic material substrates such as epoxy resin, resol, bismaleimide-triazine resin or the inorganic substrate material such as ceramic substrate, silicon substrate, is therefore also suitable as the layers cementing agent of the multilayer printed circuit board employing these substrates.
In addition, the mobility of resin combination of the present invention when being adhered on substrate, dimensional stability are suitable, operability excellence when therefore using as mulch film or when using as the layers cementing agent of multilayer printed circuit board, and can not damage the imbedibility of circuit.
In addition, the string stress of resin combination of the present invention when thermofixation is little, therefore when the layers cementing agent as multilayer printed circuit board uses, alleviates the stress residuing in layers cementing portion.Suppress the generation of the warpage in layers cementing portion thus, the reliability therefore making the through hole of multilayer printed circuit board connect improves.
In addition, when being used as the mulch film of FPC by resin combination of the present invention, the generation of warpage during thermofixation is suppressed.Therefore, the flexibility of FPC can not be damaged.
In addition, resin combination of the present invention can thermofixation below 180 DEG C, therefore as multilayer printed circuit board layers cementing agent use time or as FPC mulch film use time, the appointed condition usually used in Substrate manufacture can be applied, and have the raising of the thermotolerance such as reduction, dimensional stability, solder heat resistance of warpage, stripping strength put forward advantages of higher.
Embodiment
Below, resin combination of the present invention is described in detail.
Resin combination of the present invention contains (A) shown below ~ (F) composition as essential component.
(A) the matter average molecular weight (Mw) shown in following general formula (1) is the vinyl compound of 500 ~ 4000
In general formula (1), R 1, R 2, R 3, R 4, R 5, R 6and R 7can be hydrogen atom, halogen atom, alkyl, haloalkyl or phenyl identical or differently.Wherein, R 1, R 2, R 3, R 4, R 5, R 6and R 7be preferably hydrogen atom.
In formula ,-(O-X-O)-represent with following structural formula (2).
In structural formula (2), R 8, R 9, R 10, R 14and R 15can be halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently.Wherein, R 8, R 9, R 10, R 14and R 15be preferably the alkyl of carbon number less than 6.Wherein, R 11, R 12and R 13be preferably the alkyl of hydrogen atom, halogen atom or carbon number less than 6.
In general formula (1) ,-(Y-O)-be the a kind of structure defined with following structural formula (3) or the structure become through random arrangement with the structure of more than two kinds that following structural formula (3) defines.
In structural formula (3), R 16and R 17can be halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently.Wherein, R 16and R 17be preferably the alkyl of carbon number less than 6.
R 18and R 19can be hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently.Wherein, R 18and R 19be preferably the alkyl of hydrogen atom or carbon number less than 3.
In general formula (1), Z is the organic radical of carbon number more than 1 and sometimes comprises Sauerstoffatom, nitrogen-atoms, sulphur atom, halogen atom.Wherein, Z is preferably methylene radical.
A and b represents the integer of 0 ~ 300 and at least any one party is not 0.
C and d represents the integer of 0 or 1.Wherein, c and d is preferably 1.
Wherein, preferred: R 8, R 9, R 10, R 14and R 15for the alkyl of carbon number less than 3, R 11, R 12and R 13for the alkyl of hydrogen atom or carbon number less than 3, R 16and R 17for the alkyl of carbon number less than 3, and R 18and R 19for hydrogen atom.
In addition, in above-mentioned general formula (1)-(O-X-O)-preferably represent with following structural formula (4).
In addition, in general formula (1)-structure that becomes through random arrangement of (Y-O)-preferably have following structural formula (5) or the structure shown in following structural formula (6) or the structure shown in following structural formula (5) and the structure shown in following structural formula (6).Wherein, the structure that the structural arrangement that-(Y-O)-preferably have defines with following structural formula (6) becomes.
In resin combination of the present invention, the low-k (ε) under the region of the adhesive film that composition (A) contributes to using this resin combination to make and mulch film or excellent electrical characteristic, i.e. more than frequency 1GHz under employing the Thermocurable of layers cementing agent of this resin combination, thermotolerance and high frequency and low dielectric loss angle tangent (tan δ).
In resin combination of the present invention, as composition (A), use matter average molecular weight (Mw) in the vinyl compound shown in general formula (1) be the reason of the vinyl compound of 500 ~ 4000 as described below.
If matter average molecular weight (Mw) is less than 500, then the adhesive film using this resin combination to make and mulch film lose flexibility, become crisp and the film easily broken.In addition, when thermo-compressed or the time of being heating and curing melt viscosity excessively reduce, therefore exist infringement use the risk of the homogeneity of the thickness of the adhesive film made of this resin combination and mulch film, use this resin combination as disturbed zone during layers cementing agent between the risk of homogeneity of thickness of adhesive portion.
On the other hand, if matter average molecular weight (Mw) is more than 4000, then solvability reduces, and therefore forms problem when the preparation of resin combination.Specifically, needs long-time mixed dissolution in hot toluene when preparing varnish with solvent cut resin combination.In addition, if making film and make varnish get back to room temperature, then start recrystallization, the storage stability of varnish is deteriorated.In addition, owing to carrying out crystallization after membranization, the shape being maintained as film is thus difficult to.Therefore, the adhesive film using this resin combination to make and mulch film easily break.In addition, the film that cannot make film is become.And then the smoothness on film surface is deteriorated.
As composition (A), more preferably use matter average molecular weight (Mw) in the vinyl compound shown in general formula (1) to be the vinyl compound of 800 ~ 3500, preferably use matter average molecular weight (Mw) to be the vinyl compound of 1000 ~ 3000 further.
The method for making of the vinyl compound shown in above-mentioned general formula (1) is not particularly limited, and can manufacture in any method.Such as can obtain by also using the phase-transfer catalyst such as benzyl three normal-butyl brometo de amonio, 18-hat-6-ether to make the compound shown in 1-chloro-4-methyl-benzene and following general formula (7) react under the alkaline catalysts existence such as sodium hydroxide, salt of wormwood, sodium ethylate as required.
In general formula (7)-(O-X-O) and-(Y-O)-as above-mentioned with regard to as described in general formula (1).
Composition (B): styrene content is polystyrene-poly (ethylene/butylene) segmented copolymer of 15 ~ 35%
Composition (C): styrene content is polystyrene-poly (ethylene-vinyl/propylene) segmented copolymer of 25 ~ 40%
In resin combination of the present invention, composition (B) and (C) especially contribute to excellent electrical characteristic (low-k (ε) under the region of more than frequency 1GHz and low dielectric loss angle tangent (tan δ)), film proterties and thermotolerance under the high frequency of adhesive film and the mulch film using this resin combination to make.In addition, when using resin combination of the present invention as layers cementing agent, contribute to the excellent electrical characteristic (low-k (ε) under the region of more than 1GHz and low dielectric loss angle tangent (tan δ)) under high frequency and thermotolerance.
Wherein, compared with composition (B), the dielectric property of composition (C) is more excellent, contributes to the excellent electrical characteristic (low-k (ε) under the region of more than frequency 1GHz and low dielectric loss angle tangent (tan δ)) under high frequency.
But, compared with composition (B), the Young's modulus (modulus in tension) of the thermosetting compound of composition (C) is higher, therefore, if be used alone composition (C), string stress then during thermofixation uprises, and therefore needs composition (B) to combinationally use.
Therefore, in resin combination of the present invention, use composition (B) and (C) with specific mixing ratio as described below.
In the present invention, the composition (B) in resin combination and the mass ratio of (C) are (B)/(C)=more than 1.00 and less than 4.00.
If (B)/(C)=less than 1.00, although then obtain required bonding strength, but the Young's modulus of thermosetting compound uprises, therefore use the string stress during thermofixation of the adhesive film made of resin combination and mulch film to uprise, easily produce warpage.In addition, when use resin combination is as layers cementing agent, if the stress deformation in layers cementing portion becomes large, then the reliability reduction of warpage and through hole connection is produced.
On the other hand, if (B)/(C)=more than 4.00, the Young's modulus step-down of then thermosetting compound, although the generation of the warpage in the layers cementing portion therefore can suppress to use the generation of the warpage in the adhesive film made of resin combination and mulch film, adopting resin combination to obtain, cannot obtain required bonding strength.
If (B)/(C)=more than 1.00 and less than 4.00, then the Young's modulus of thermosetting compound can not uprise, and can obtain required bonding strength.
The mass ratio of composition (B) and (C) is more preferably (B)/(C)=more than 1.5 and less than 3.5.
But composition (B) and (C) need to use styrene content to be in composition (B) and (C) of above-mentioned specified range.
If the styrene content of composition (B) is less than 15%, then there is the problem inferior with the consistency of other compositions of resin combination.
On the other hand, if the styrene content of composition (B) is more than 35%, then use resin combination when making adhesive film or mulch film, there is the problem cracking in cured films etc. and be difficult to film forming.
If the styrene content of composition (C) is less than 25%, then there is the problem inferior with the consistency of other compositions of resin combination.
On the other hand, if the styrene content of composition (C) is more than 40%, then use resin combination when making adhesive film or mulch film, exist and the problem being difficult to film forming such as to crack in cured films.
Composition (D): epoxy resin
In resin combination of the present invention, composition (D) contributes to Thermocurable when using the adhesive film made of this resin combination and mulch film and used as layers cementing agent by this resin combination and cementability.
In addition, by using composition (D), thus composition (E) is improved to the solvability of the low boiling point solvents such as toluene, methylethylketone, methyl iso-butyl ketone (MIBK).
In resin combination of the present invention, the content of composition (D) counts 1 ~ 10 quality % with the mass percent of the total mass relative to composition (A) ~ (E).
If composition (D) containing quantity not sufficient 1 quality %, then cementability when existing the adhesive film using this resin combination to make and mulch film and used as layers cementing agent by this resin combination becomes the problem such as insufficient.
If the content of composition (D) is more than 10 quality %, then compatibility poor, and required dielectric loss angle tangent (tan δ) value cannot be obtained.In addition, the adhesive film using this resin combination to make and the discharge of mulch film when thermofixation become excessive.And then, because the ratio that composition (D) is shared in whole composition becomes many, the characteristic of the composition (D) that therefore thermotolerance is inferior impacts the adhesive film using this resin combination to make and mulch film and the layers cementing portion entirety that uses this resin combination to obtain.Therefore, there is the risk that the thermotolerance in the layers cementing portion using the adhesive film made of this resin combination and mulch film and employ this resin combination or solidified nature reduce.
Resin combination of the present invention is more preferably containing the composition (D) relative to the total mass of composition (A) ~ (E) being 1 ~ 5 quality %.
The epoxy resin used as composition (D) is not particularly limited, and can use the various epoxy resin such as phenolic resin varnish type epoxy resin, bisphenol A type epoxy resin, bisphenol f type epoxy resin, biphenyl type epoxy resin, fluorenes type epoxy resin, naphthalene type epoxy resin.
But when using in molecule the epoxy resin of epoxy resin as composition (D) that there is hydroxyl, if the content of epoxy resin increases, then under the impact of the polarity based on hydroxyl, the specific inductivity of resin combination rises.
Therefore, the epoxy resin of composition (D) is preferably used in the epoxy resin that there is not hydroxyl in molecule.In above-mentioned epoxy resin, the suitable mutually therewith biphenyl type epoxy resin, fluorenes type epoxy resin, the naphthalene type epoxy resin that there is not hydroxyl in addition in the molecule.
By the epoxy resin using these to there is not hydroxyl in the molecule, the rising of specific inductivity can be suppressed.
Be explained, in above-mentioned epoxy resin, can use any a kind, also two or more kinds may be used.
From the reason of the mechanical characteristics after Thermocurable, cementability, solidification, the epoxy resin preferred number average molecular weight (Mn) used as composition (D) is the epoxy resin of 150 ~ 2500.
Composition (E): bismaleimides
In mulch film of the present invention, the bismaleimides of composition (E) and the vinyl compound effect of composition (A), can carry out being heating and curing of the adhesive linkage of mulch film at lower temperatures.
This be due to: in the present invention, change from the view point of the imparting of the maintenance of dielectric property, bonding strength and high Tg (second-order transition temperature), preferably use bismaleimides.
The use level of the bismaleimides of composition (E) is preferably decided by the equivalence ratio of the vinyl of the vinyl compound relative to composition (A).Specifically, relative to vinyl 1 equivalent of the vinyl compound of composition (A), the bismaleimides of composition (E) is 0.1 ~ 3 equivalent, is preferably 0.5 ~ 1.5 equivalent, is more preferably 0.8 ~ 1.3 equivalent.
In resin combination of the present invention, the resin material that composition (A), (E) are Thermocurable, composition (B), (C) are thermoplastic resin material.
In the present invention, the resin material of these Thermocurables and the mixing ratio of thermoplastic resin material bring impact to the physical property of resin combination.Therefore, (composition (A), (E)) and (composition (B), (C)) is used with specific mixing ratio as described below.
Be explained, the epoxy resin of composition (D) is also the resin material of Thermocurable, but as mentioned above, the content of composition (D) is few to 1 ~ 10 quality % with the mass percent of the total mass relative to composition (A) ~ (E), if therefore use (composition (A), (E)) and (composition (B), (C)) with specific mixing ratio as described below, then can ignore the impact that composition (D) brings to the physical property of resin combination of the present invention.
In resin combination of the present invention, the mass ratio of the total amount of the total amount of composition (A), (E) and composition (B), (C) is (A+E)/(B+C)=more than 0.81 and less than 1.00.
If the mass ratio of each composition (A+E)/(B+C)=less than 0.81, then cannot obtain required bonding strength.
On the other hand, if (A+E)/(B+C)=more than 1.00, the Young's modulus of then thermosetting compound uprises, therefore easily produce the warpage in the adhesive film using resin combination to make and mulch film, adopt resin combination to obtain layers cementing portion in warpage.
Composition (F): the exothermic peak utilizing means of differential scanning calorimetry (DSC) to measure to obtain is more than 100 DEG C and the organo-peroxide of less than 180 DEG C
In resin combination of the present invention, composition (F) promotes the reaction of the vinyl compound used as composition (A), can carry out low-temperature curing below 180 DEG C.In addition, the effects such as the raising of the thermotolerance such as reduction, dimensional stability, solder heat resistance of warpage, the raising of stripping strength are also played.
Utilize DSC to measure the exothermic peak obtained to refer to the exothermic peak obtained according to following step measurements in the present invention.
Exothermic peak is read with the heat up DSC curve that obtains of the speed of 5 DEG C/min from utilizing differential scanning calorimeter.In the present invention, using the temperature of summit as the exothermic peak of object.
If the exothermic peak utilizing DSC to measure to obtain is less than 100 DEG C, then can carry out reacting and solidifying because of thermal history when forming adhesive film or mulch film by resin combination.Therefore, binding function is lost.In addition, when resin combination of the present invention is used as the layers cementing agent of multilayer printed circuit board, also need to make solvent evaporates and carry out drying after coating comprises the varnish of resin combination, understand the solidification caused by reason thermal history and lose binding function therefore equally with when formation adhesive film or mulch film.
If the exothermic peak utilizing DSC to measure to obtain is more than 180 DEG C, then the thermal curing time below 180 DEG C is elongated.
In the present invention, the exothermic peak utilizing DSC to measure to obtain is more preferably at 120 ~ 180 DEG C.
In the present invention, as the organo-peroxide of composition (F), can use: different nonanoyl superoxide, decanol peroxide, lauroyl peroxide, to chlorobenzoyl peroxide, two (3,5,5-trimethyl acetyl base) the diacyl peroxide class such as superoxide; The peroxy ketal classes such as 2,2-bis-(4,4-bis--(two-t-butyl peroxy) cyclohexyl) propane; Peroxy two carbonates such as two-3-methoxybutyl peroxydicarbonate, dicyclohexyl peroxydicarbonate; T-butyl peroxybenzoate, tert-butyl peroxy acetate, t-butyl peroxy-2-ethylhexanoate, tert-butylperoxy isobutyrate, t-butyl peroxy valerate, tertiary butyl diperoxy adipic acid ester, cumyl peroxide neodecanoic acid ester, t-butyl peroxybenzoate, 1,1,3,3-tetramethyl butyl peroxy-2-ethylhexanoate, 2, the peroxyesters such as 5-dimethyl-2,5 two (benzoylperoxy) hexane; The ketone peroxide such as methyl ethyl ketone peroxide, Cyclohexanone peroxides class; Ditertiary butyl peroxide, diisopropylbenzyl superoxide, tert butyl isopropyl benzene peroxide, 1,1-bis-(tertiary hexyl peroxy)-3, the dialkyl peroxide classes such as 3,5-trimethyl-cyclohexane, two tertiary hexyl superoxide, two (2-tert butylperoxyisopropyl) benzene; Isopropyl benzene hydroxyl peroxide, tertbutyl peroxide, to hydroperoxide kinds etc. such as menthane hydrogen peroxide.
Wherein, preferred peroxyesters and dialkyl peroxide class, from the exothermic peak making to utilize DSC to measure and obtain at the good aspect of the storage stability of 120 ~ 180 DEG C and composition, particularly preferably t-butyl peroxybenzoate, 1,1,3,3-tetramethyl butyl peroxy-2-ethylhexanoate and two (2-tert butylperoxyisopropyl) benzene.
In resin combination of the present invention, the content of composition (F) counts 0.1 ~ 10 quality % with the mass percent of the content relative to composition (A).
If composition (F) containing quantity not sufficient 0.1 quality %, then promote that the effect of the reaction of the vinyl compound used as composition (A) becomes insufficient.Therefore, the thermofixation below 180 DEG C cannot be realized.
On the other hand, if the content of composition (F) is more than 10 quality %, then electric properties deteriorate in high frequency.
The content of composition (F) is more preferably 1 ~ 10 quality % with the mass percent of the content relative to composition (A).
Resin combination of the present invention can also containing the curing catalysts as composition (G) except mentioned component (A) ~ (F).This curing catalysts plays a role as the curing catalysts of the epoxy resin of composition (D).
As composition (G) as long as the curing catalysts used is the curing catalysts of epoxy resin, be then not particularly limited, known curing catalysts can be used.Include, for example imidazoles system curing catalysts, amine system curing catalysts, phosphorus system curing catalysts etc.
As imidazoles system curing catalysts, the imidazolium compoundss such as glyoxal ethyline, 2-undecyl imidazole, 1-cyano ethyl-2-undecyl imidazole, 2-heptadecyl imidazole, 2-ethyl-4-methylimidazole, 1-cyano ethyl-2-ethyl-4-imidazoles, 2-phenylimidazole, 2-phenyl-4-methylimidazole can be enumerated.Wherein, preferred 2-ethyl-4-methylimidazole, 1-cyano ethyl-2-undecyl imidazole and 1-cyano ethyl-2-ethyl-4-imidazoles.
As amine system curing catalysts, can enumerate: the triaizine compounds such as 2,4-diamino-6-(2 '-methylimidazolyl-(1 ')) ethyl-s-triazine; The tertiary amine compounds such as 1,8-diazabicyclo [5,4,0] hendecene-7 (DBU), triethylenediamine, benzyl dimethyl amine, trolamine.Wherein, preferred 2,4-diamino-6-(2 '-methylimidazolyl-(1 ')) ethyl-s-triazine.
In addition, as phosphorus system curing catalysts, triphenylphosphine, tributylphosphine, three (p-methylphenyl) phosphine, three (nonyl phenyl) phosphine etc. can be enumerated.
Be explained, in above-mentioned curing catalysts, can use any a kind, also two or more kinds may be used.The significant quantity of curing catalysts is different according to the kind of curing catalysts.According to the kind of curing catalysts, its significant quantity is shown below.
When imidazoles system curing catalysts, amine system curing catalysts, its significant quantity counts 0.01 ~ 5 quality % with the mass percent of the total mass of the whole compositions relative to resin combination, is more preferably 0.05 ~ 3 quality %.
When phosphorus system curing catalysts, its significant quantity counts 0.01 ~ 10 quality % with the mass percent of the total mass of the whole compositions relative to resin combination, is more preferably 0.05 ~ 5 quality %.
Resin combination of the present invention can also contain other compositions as required.As the concrete example of this kind of composition, silane coupling agent, defoamer, flow modifier, film adjuvants, dispersion agent etc. can be enumerated.
Resin combination of the present invention can utilize customary way to manufacture.Such as, under the condition of presence or absence solvent, heating, vacuum mixing tank is utilized to mix mentioned component (A) ~ composition (F) (also comprising these any compositions when resin combination contains mentioned component (G) or other any compositions).
Mentioned component (A) ~ composition (F) can according to reaching the required solvent strength being dissolved into (also comprising these any composition when resin combination contains mentioned component (G) or other any compositions) regulation containing proportional mode, dropped into specified amount in the reactor being heated to 10 ~ 80 DEG C, while make it rotate with rotating speed 100 ~ 1000rpm, while carry out the normal pressure mixing of 3 hours, (maximum 1Torr) further mix and blend 30 ~ 60 minutes afterwards under vacuo.
Resin combination of the present invention has proper characteristics shown below.
The thermosetting compound electrical characteristic in high frequency of resin combination of the present invention are excellent.Specifically, the specific inductivity of thermosetting compound under the region of more than frequency 1GHz (ε) of resin combination is preferably less than 3.0, is more preferably less than 2.5.In addition, the dielectric loss angle tangent (tan δ) under the region of more than frequency 1GHz is more preferably less than 0.01, and more preferably less than 0.005.
By making the specific inductivity under the region of more than frequency 1GHz (ε) and dielectric loss angle tangent (tan δ) be in above-mentioned scope, the electrical signal loss under the region of more than frequency 1GHz can be reduced in.
From the aspect improving bonding strength and string stress when alleviating thermofixation, the modulus in tension of the thermosetting compound of resin combination of the present invention is preferably 150 ~ 450MPa.
If modulus in tension is below 450MPa, then alleviate string stress during thermofixation, therefore play following effect.
When the layers cementing agent as multilayer printed circuit board uses, alleviate the stress residuing in layers cementing portion.Thus, suppress the generation of the warpage in layers cementing portion, the reliability therefore making the through hole of multilayer printed circuit board connect improves.
In addition, when being used as the mulch film of FPC by resin combination of the present invention, the generation of warpage during thermofixation is suppressed.Therefore, the flexibility of FPC can not be damaged.
Be explained, for resin combination of the present invention, as with measured by the step recorded in embodiment described later, the amount of warpage of the thermosetting compound of the film that 100mm is square is preferably below 15mm, is more preferably below 10mm.
But if the modulus in tension of thermosetting compound is too low, then the bonding strength of resin combination reduces, and therefore needs for more than 150MPa.
The modulus in tension of resin combination of the present invention more preferably its thermosetting compound is 200 ~ 400MPa.
The lowest melt viscosity of resin combination of the present invention when its thermofixation, specifically when the temperature province of 100 ~ 180 DEG C is preferably 1000 ~ 50000Pas.
If lowest melt viscosity during thermofixation is above-mentioned scope, then mobility during thermofixation is in suitable state, therefore preferably.Specifically, when using the thermo-compressed of the adhesive film made of resin combination or mulch film or when using resin combination as thermo-compressed during layers cementing agent, good fluidity, therefore becomes good to the imbedibility of minor gap wiring pattern.
At this, lowest melt viscosity is the Schwellenwert of viscosity when making this adhesive film melting when heated resin composition.
If the lowest melt viscosity when the temperature province of 100 ~ 180 DEG C is less than 1000Pas, then mobility during thermofixation is too high, therefore there is the risk changed at the thickness in the front and back adhesive film of thermofixation or the thickness of mulch film or layers cementing portion.
If the lowest melt viscosity when the temperature province of 100 ~ 180 DEG C is more than 50000Pas, then exists and insufficient risk is become to the imbedibility of minor gap wiring pattern, need to increase the pressurization pressure applied when thermo-compressed.
The lowest melt viscosity of resin combination of the present invention more preferably when the temperature province of 100 ~ 180 DEG C is 2000 ~ 20000Pas.
From the view point of thermotolerance or the long-term reliability of thermosetting compound, the second-order transition temperature of the thermosetting compound of resin combination of the present invention is preferably more than 160 DEG C.
The thermosetting compound of resin combination of the present invention has sufficient bonding strength.Specifically, more than 5N/cm is preferably to the stripping strength to roughening of copper foil face (180 degree of strippings) that the thermosetting compound adding resin combination records according to JISC6471, is more preferably more than 6N/cm.
In addition, the stripping strength to polyimide film (180 degree of strippings) recorded according to JISC6471 is preferably more than 5N/cm, is more preferably more than 6N/cm.
Adhesive film of the present invention and mulch film can be utilized known method to obtain by resin combination of the present invention.Such as can make varnish with solvent cut resin combination of the present invention, be coated at least one side of supporter, and after making its drying, provide with the form of the film with supporter or the film after peeling off from supporter.
As the solvent that can be used as varnish, can enumerate: the ketone such as methylethylketone, methyl iso-butyl ketone (MIBK); The aromatic solvent such as toluene, dimethylbenzene; The high boiling solvent such as dioctyl phthalate (DOP), dibutyl phthalate etc.The usage quantity of solvent is not particularly limited, can for all the time used amount, but is preferably 20 ~ 90 quality % relative to solids component.
Supporter is suitably selected according to form needed in the manufacture method of film, is not particularly limited, can enumerates such as: the tinsel such as copper, aluminium; The film carrier etc. of the resin such as polyester, polyethylene.When to provide adhesive film of the present invention from the form of the film after supporter stripping, preferably supporter silicone compounds etc. is carried out demoulding process.
The method of coating varnish is not particularly limited, such as seam die head mode, intaglio plate mode, doctor knife coater mode etc. can be enumerated, suitably can select according to the thickness etc. of required film, but from designing the aspect of the thickness of film compared with unfertile land, particularly preferably intaglio plate mode.Be coated with and carry out in the mode making the thickness of the dry rear film formed reach desired thickness.As long as be those skilled in the art, this thickness can be derived by solvent.
The thickness of adhesive film of the present invention and mulch film suitably can design based on characteristics such as the physical strengths required by purposes, but, being generally 1 ~ 100 μm, when requiring filming, being preferably 1 ~ 30 μm.
Dry condition suitably can design according to the kind of the solvent used in varnish and amount, the usage quantity of varnish, the thickness etc. of coating, be not particularly limited, such as, can carry out under normal atmosphere at 60 ~ 100 DEG C.
The use step of adhesive film of the present invention as shown below.
Using in the bonding object of adhesive film of the present invention, an object loaded adhesive film of the present invention by bonding plane after, load another object to make the mode by bonding plane contacts with the exposed surface of adhesive film.At this, when using the adhesive film of band supporter, to make the exposed surface of adhesive film load adhesive film with the mode contacted by bonding plane of an object, and this adhesive film is needed in sticky surface.At this, temperature during transfer printing can be such as 130 DEG C.
Then, on the face of adhesive film of exposing by peeling off supporter during transfer printing to make the mode by bonding plane contacts with the exposed surface of adhesive film load another object.After implementing these steps, make it carry out thermo-compressed with specified temperature and specified time, afterwards, make it be heating and curing.
Temperature during thermo-compressed is preferably 100 ~ 180 DEG C.The time of thermo-compressed is preferably 0.5 ~ 10 minute.
The temperature be heating and curing is preferably 150 ~ 180 DEG C.The time of being heating and curing is preferably 30 ~ 120 minutes.
Be explained, also can replace the resin combination after using membranization in advance and implement to make varnish with solvent cut resin combination of the present invention, and this varnish is coated an adhering object thing by bonding plane, after making its drying, implement the step of an above-mentioned mounting object.
Adhesive film of the present invention also may be used for the layers cementing of multilayer printed circuit board.Now, above-mentioned bonding object becomes the substrate of each layer forming multilayer printed circuit board.Be explained, for the layers cementing of multilayer printed circuit board, also can replace the resin combination after using membranization in advance and use with the varnish made by solvent cut resin combination of the present invention.
Use adhesive film of the present invention or varnish to carry out the multilayer printed circuit board of layers cementing, the stress residuing in layers cementing portion can be alleviated.Thus, suppress the generation of the warpage in layers cementing portion, the reliability therefore making the through hole of multilayer printed circuit board connect improves.In addition, the excellent in dimensional stability in layers cementing portion.
The substrate forming each layer of multilayer printed circuit board is not particularly limited, and can use any one in the organic substrates such as epoxy resin, resol, bismaleimide-triazine resin or the inorganic substrate such as ceramic substrate, silicon substrate.In addition, the resin substrate being suitable for FPC of the present invention described later can also be used.
Then, the use step of mulch film of the present invention is shown.
For mulch film of the present invention, the position that the prescribed position of the resin substrate of the band wiring obtained wiring pattern is formed at interarea, the coating epiphragma being namely formed with the side of wiring pattern cover, after configuring this mulch film, with specified temperature and specified time, thermo-compressed is carried out to it.
Temperature during interim crimping in thermo-compressed is preferably 100 ~ 180 DEG C.The time of interim crimping is preferably 0.5 ~ 10 minute.
The temperature be heating and curing is preferably 150 ~ 180 DEG C.The time of being heating and curing is preferably 30 ~ 120 minutes.
In mulch film of the present invention, the generation of warpage when can suppress thermofixation.
Flexible printed circuit board of the present invention (FPC) is after the wiring pattern side of the resin substrate of the band wiring obtained wiring pattern is formed at interarea configures mulch film of the present invention, be heating and curing with specified temperature and specified time, the printed circuit board (PCB) that the resin substrate that band is connected up is integrated with mulch film.
The resin substrate used in FPC of the present invention is preferred: the electrical characteristic of high-frequency region are excellent, namely at the region of more than frequency 1GHz display low-k (ε) and low dielectric loss angle tangent (tan δ).As the concrete example of this kind of resin substrate, can enumerate with any one in liquid crystalline polymers (LCP), tetrafluoroethylene (PTFE), polyimide (PI) and PEN (PEN) is the resin substrate of principal constituent.
In addition, as another concrete example of resin substrate being suitable for FPC of the present invention, can enumerate with the vinyl compound shown in (a) following general formula (1) and (b) rubber and/or thermoplastic elastomer is the resin substrate of principal constituent.
The vinyl compound shown in above-mentioned formula (1) of composition (a) is as above-mentioned just as described in resin combination of the present invention.
Be the resin substrate of principal constituent with the vinyl compound shown in (a) above-mentioned general formula (1) and (b) rubber and/or thermoplastic elastomer, there is the formation same with resin combination of the present invention, and display low-k, low dielectric loss angle tangent.Therefore, such as, when combining with the layers cementing agent or mulch film that employ resin combination of the present invention, the printed base plate of high frequency characteristics excellence can be made.
In addition, owing to having the formation same with resin combination of the present invention, therefore high with the bonding strength of the layers cementing agent or mulch film that employ resin combination of the present invention.
Composition (b): rubber and/or thermoplastic elastomer,
The above-mentioned concrete example being suitable for the resin substrate of FPC of the present invention, containing at least one party in rubber and thermoplastic elastomer as composition (b).Resin substrate can containing both rubber and thermoplastic elastomer.
As the rubber of composition (b), the rubber-like such as styrene butadiene rubbers, isoprene-isobutylene rubber, divinyl rubber, acrylic rubber can be enumerated.These rubber-like can be used alone or two or more kinds may be used.
On the other hand, as thermoplastic elastomer, styrene series thermoplastic elastomer, olefin series thermoplastic elastomer, Polyester thermoplastic elastomer etc. can be enumerated.Thermoplastic elastomer can be used alone or two or more kinds may be used.
As composition (b), from making the reasons such as the flexibility of resin substrate is excellent, preferred thermoplastic elastomer, particularly preferably styrene series thermoplastic elastomer.
As the concrete example of styrene series thermoplastic elastomer, styrene-butadiene block copolymer can be enumerated, styrene isoprene styrene block copolymer (SIS) or the multipolymer that a part of hydrogenation of the double bond of these multipolymers is obtained, more specifically, styrene-butadiene-styrene block copolymer (SBS) can be enumerated, styrene isoprene styrene block copolymer (SIS) (SIS), styrene-ethylene-butylene-styrene block copolymer (SEBS), styrene ethylene-propylene-styrene block copolymer (SEEPS) etc.Wherein, preferred SBS, SEBS.
When using styrene series thermoplastic elastomer as composition (b), preferred matter average molecular weight is the styrene series thermoplastic elastomer of 20000 ~ 250000.In addition, with the consistency of composition (a) good in, the styrene content in styrene series thermoplastic elastomer is preferably 15 ~ 60 quality %, is more preferably 20 ~ 50 quality %.Be explained, matter average molecular weight utilizes GPC and uses the value that the working curve obtained based on polystyrene standard is tried to achieve.
As the concrete example of styrene series thermoplastic elastomer, styrene-butadiene block copolymer " JSRTR " series of JSR Corp., styrene-isoprene block copolymer " JSRSIS " series etc. can be enumerated.
And then, if use the composition (B) of above-mentioned resin combination of the present invention, (C) as composition (b) and the mass ratio of composition (B) and (C) is (B)/(C)=more than 1.00 and less than 4.00, then contribute to excellent electrical characteristic in high frequency, the Young's modulus of thermosetting compound can not be improved simultaneously, and with form copper excellent in adhesion of wiring pattern.
And then, if add the composition (D) of above-mentioned resin combination of the present invention, then can improve Thermocurable and improve the cementability with the copper forming wiring pattern, if add the composition (E) of above-mentioned resin combination of the present invention, then dielectric property can be kept, give bonding strength, and realize high Tg (second-order transition temperature) change.
In addition, the composition (F) of above-mentioned resin combination of the present invention can be added.By added ingredients (F), the low-temperature curing of the resin substrate using composition (a) can be realized.The equipment, the condition that usually use in Substrate manufacture can be applied thus.And then, can warpage be reduced, improve the thermotolerance such as dimensional stability, solder heat resistance, and improve stripping strength.
Be suitable for the concrete example of the resin substrate of above-mentioned FPC of the present invention, on the basis of above-mentioned composition (a), (b), preferably also contain the silane coupling agent as composition (c).The silane coupling agent of composition (c) contributes to the stickiness of resin substrate and wiring pattern when wiring pattern being needed on resin substrate.
Be suitable in the concrete example of the resin substrate of FPC of the present invention above-mentioned, composition (a) is preferably 3:7 ~ 7:3 with the mass ratio of composition (b), is more preferably 4:6 ~ 6:4.
Above-mentioned] be suitable for the concrete example of the resin substrate of FPC of the present invention, can containing any composition except above-mentioned composition (a) ~ (c).As the concrete example of this kind of any composition, the weighting agent used for the object of the physical strength improving resin substrate can be enumerated.As the concrete example of this kind of weighting agent, can enumerate: the mineral compound such as silicon-dioxide, aluminum oxide, titanium oxide, boron nitride, ferric oxide; Or the organic fillers such as carbon.
Containing weighting agent as any composition time, weighting agent is preferably 9:1 ~ 1:9 relative to the mass ratio of the total amount of composition (a) ~ (c), is more preferably 8:2 ~ 2:8, more preferably 7:3 ~ 3:7.
In addition, the above-mentioned resin substrate being suitable for FPC of the present invention, can for improve resin substrate physical strength object and together with above-mentioned weighting agent or replace the organic fibre of above-mentioned weighting agent and inorganic fibre, aramid fiber and so on containing glass fibre, carbon fiber and so on.
Embodiment
Below, the present invention will be described in detail to utilize embodiment, but the present invention is not limited to the examples.
(embodiment 1 ~ 9, comparative example 1 ~ 12)
Sample making and measuring method
Measure according to the mixing ratio (quality %) shown in following table and after coordinating each composition, dropped in the reactor being heated to 70 DEG C, while make it rotate with rotating speed 300rpm, while carry out the normal pressure mixing of 3 hours.When adding solidifying agent, add solidifying agent after the cooling period.
The varnish comprising the resin combination so obtained is coated the one side of supporter (implementing the PET film of demoulding process), make it 100 DEG C of dryings, obtain the adhesion film being with supporter thus.
Be explained, the abbreviation in table represents following implication respectively.
Composition (A)
OPE2200: oligomeric phenylate (vinyl compound shown in above-mentioned general formula (1)) (Mn=2200), Mitsubishi Gas Chemical Co., Ltd's system
Composition (B)
TuftecH1052: polystyrene-poly (ethylene/butylene) segmented copolymer (vinylbenzene amount 20%), Asahi Kasei Corporation's system
TuftecH1031: polystyrene-poly (ethylene/butylene) segmented copolymer (vinylbenzene amount 30%), Asahi Kasei Corporation's system
Composition (B ')
TuftecH1221: polystyrene-poly (ethylene/butylene) segmented copolymer (vinylbenzene amount 12%), Asahi Kasei Corporation's system
Septon8104: polystyrene-poly (ethylene/butylene) segmented copolymer (vinylbenzene amount 60%), Kuraray Co., Ltd. system
Composition (C)
Septon4044: polystyrene-poly (ethylene-vinyl/propylene) segmented copolymer (vinylbenzene amount 32%), Kuraray Co., Ltd. system
Composition (BC ')
TR2003: polystyrene-polybutadiene segmented copolymer (phenylethylene/butadiene=43/57), JSR Corp.'s system
Composition (D)
NC3000H: biphenyl type epoxy resin, Nippon Kayaku K. K's system
HP4032D: naphthalene type epoxy resin, Dainippon Ink Chemicals's system
828EL: bisphenol A type epoxy resin, Mitsubishi chemical Co., Ltd's system
Composition (E)
BMI-70: bismaleimides, KI change into Co., Ltd.'s system
Composition (F)
PerbutylZ: t-butyl peroxybenzoate, Japan Oil Co's system, exothermic peak 140 ~ 170 DEG C
PerbutylP: two (2-tert butylperoxyisopropyl) benzene, Japan Oil Co, exothermic peak 160 ~ 180 DEG C
PeroctaO:1,1,3,3-tetramethyl butyl peroxy-2-ethylhexanoate, Japan Oil Co's system, exothermic peak 120 ~ 130 DEG C
Composition (F ')
PeroylOPP: two (2-ethylhexyl) peroxydicarbonate, Japan Oil Co, exothermic peak 80 ~ 100 DEG C
NofmerBC-90:2,3-dimethyl-2,3-diphenyl butane, Japan Oil Co, exothermic peak more than 200 DEG C
Composition (G)
C11ZCN:1-cyano ethyl-2-undecyl imidazole, Shikoku Chem's system
2E4MZ:2-ethyl-4-methylimidazole, Shikoku Chem's system
1B2PZ:1-benzyl-2-phenylimidazole, Shikoku Chem's system
TPP-MK: tetraphenylphosphoniphenolate four ptolylboronic acid salt, Hokko Chemical Industry Co., Ltd.'s system
Specific inductivity (ε), dielectric loss angle tangent (tan δ): adhesion film is heating and curing at 180 DEG C, after it is peeled off from supporter, cut out test film (40 ± 0.5mm × 100 ± 2mm) from this adhesion film, measure thickness.Test film is curled the tubular of growth 100mm, below diameter 2mm, utilize rhumbatron perturbation method (10GHz) to determine specific inductivity (ε) and dielectric loss angle tangent (tan δ).
Modulus in tension: adhesion film is heating and curing at 180 DEG C, after it being peeled off from supporter, cuts out 5 test films (25 ± 0.5mm × 220 ± 2mm), determines thickness from this adhesion film along MD direction.This test film clamping fixture is fixed on universal testing machine with wide 170mm, measures to stroke 5mm with draw speed 1mm/min.The mean value of N=5 is set to measured value.
Amount of warpage: the Copper Foil (the Copper Foil CF-T8 of Fukuda Metal Foil & POwder Co., Ltd.) of thickness 18 μm is cut out 100 ± 0.5mm square, utilizes pressing machine to be crimped on Copper Foil one side the adhesion film cutting into same size and makes its be heating and curing (180 DEG C, 60min, 1MPa).Peel off supporter, by be pasted with adhesion film face down be placed in smooth desk horizontal plane on, measure because of cure shrinkage produce amount of warpage.That is, amount of warpage is the maximum value of the height at the position that central authorities float from the horizontal plane of desk to film.
Stripping strength (Cu): the alligatoring face dried adhesion film hot pressing being connected to Copper Foil (CF-T8, Fukuda Metal Foil & POwder Co., Ltd.'s system, thickness 18 μm), make its (thermo-compressed: 130 DEG C 3 minutes that is heating and curing afterwards, be heating and curing: 180 DEG C × 1hr) after, determine stripping strength (180 degree of strippings) according to JISC6471.From copper-clad surface with 10mm width cutting adhesion film, utilize universal testing machine to peel off, determine stripping strength (180 degree of strippings).
Stripping strength (PI): dried adhesion film hot pressing is connected to polyimide film (K100EN, Dong Li Dupont Kabushiki Kaisha system, 25 μm), make its (thermo-compressed: 130 DEG C 3 minutes that is heating and curing afterwards, be heating and curing: 180 DEG C × 1hr) after, determine stripping strength (180 degree of strippings) according to JISC6471.Cut adhesion film from the face of polyimide film with 10mm width, utilize universal testing machine to peel off, determine stripping strength (180 degree of strippings).
Dimensional stability (according to JISC6471): utilize thermo-compressed (180 DEG C, 60 minutes, 1MPa) Copper Foil of fitting on the two sides of the adhesion film utilizing above-mentioned method to obtain, make the sample of 200mm × 250mm.The hole of diameter 2mm is offered at 4 angles of sample, first the longitudinal direction in adjacent hole and the interval of transverse direction is measured, then, by after whole for the Copper Foil on surface facet etch to it with 80 DEG C of drying treatment 30 minutes, afterwards, again measure the longitudinal direction in adjacent hole and the interval of transverse direction, then try to achieve the size changing rate of vertical and horizontal according to the change at the interval in the hole before and after process.Carry out the thermal treatment of 30 minutes again at 150 DEG C, carry out mensuration similar to the above, try to achieve the size changing rate of vertical and horizontal.The mean value of the size changing rate of vertical and horizontal is described in table.
Solder heat resistance (solder float test): utilize thermo-compressed (180 DEG C, 60 minutes, 1MPa) Copper Foil of fitting on the two sides of the adhesive film utilizing above-mentioned method to obtain, makes the sample of 50mm × 50mm.Make it float over from 290 DEG C each raising in the solder bath of the temperature of 10 DEG C 30 seconds, evaluate with or without expansion.The numerical value of the temperature than low 10 DEG C of the temperature produced when expanding is described in table.
Be explained, to obtaining below amount of warpage 15mm and stripping strength 5N/ cthe composition of the result of more than m, does not carry out the evaluation of dimensional stability and solder heat resistance.
Table 1
Table 2
Table 3
Table 4
In embodiment 1 ~ 9, the electrical characteristic (specific inductivity (ε), dielectric loss angle tangent (tan δ)) of amount of warpage, high frequency, modulus in tension, stripping strength, dimensional stability, solder heat resistance are all excellent.Increasing in the embodiment 5 of B/C compared with embodiment 1, modulus in tension can be reduced.Further increasing in the embodiment 6 of B/C than embodiment 5, modulus in tension can be reduced further.
In addition, decrease compared with embodiment 1 (D) composition epoxy resin content embodiment 8 in, dielectric loss angle tangent (tan δ) can be reduced further.
At replacement composition (B), (C) and be used as in the comparative example 1 of the polystyrene-polybutadiene segmented copolymer of thermoplastic elastomer, amount of warpage is large.In addition, dimensional stability and solder heat resistance inferior.
Do not containing in the comparative example 2 of composition (B), modulus in tension uprises, and amount of warpage also becomes large.In addition, dimensional stability and solder heat resistance inferior.
Do not containing in the comparative example 3 of composition (C), stripping strength is low.
Be that in the comparative example 4 of (A+E)/(B+C)=less than 0.81, stripping strength is low at the mass ratio of each composition.
Be that in the comparative example 5 of (A+E)/(B+C)=more than 1.00, amount of warpage is large at the mass ratio of each composition.
In the comparative example 6 of mass ratio (B)/(C)=less than 1.00 of composition (B) and (C), amount of warpage is large.
In the comparative example 7 of mass ratio (B)/(C)=more than 4.00 of composition (B) and (C), stripping strength is low.
Do not containing in the comparative example 8 of composition (F), dimensional stability is inferior.
Employ in the comparative example 9 of the polystyrene-poly of styrene content less than 15% (ethylene/butylene) segmented copolymer in replacement composition (B), stripping strength (PI) is low.In addition, dimensional stability and solder heat resistance inferior.
Employ in the comparative example 10 of the polystyrene-poly of styrene content more than 35% (ethylene/butylene) segmented copolymer in replacement composition (B), amount of warpage is large.And dimensional stability is inferior.
In comparative example 11 more than 180 DEG C of the exothermic peak of composition (F), dimensional stability is inferior.
In comparative example 12 less than 100 DEG C of the exothermic peak of composition (F), stripping strength cannot be measured.
The FPC that will be principal constituent using composition (a), (b) is as the making method of the printed circuit board (PCB) of substrate
The resin combination containing following compositions is employed in the making of the resin substrate of FPC.
Composition (a): OPE2st: oligomeric phenylate (vinyl compound shown in above-mentioned general formula (1)) (Mn=2200), Mitsubishi Gas Chemical Co., Ltd's system 50.0 parts
Composition (b): polystyrene-polybutadiene segmented copolymer (JSR Corp.'s system: " TR2003 ": matter average molecular weight about 100,000, styrene content 43 quality %) 50.0 parts
Composition (c) silane coupling agent
γ-acryloxypropyl Trimethoxy silane (" KBM-5103 ", Shin-Etsu Chemial Co., Ltd's system) 0.5 part
Use Three-OneMotor (Xin Dong science Co., Ltd. system, BLW1200) with the above-mentioned each composition of circumferential speed 400rpm dry type mixing, be prepared into resin combination.This resin combination is joined in solvent toluene, carries out heated and stirred, be prepared into varnish (solid component concentration about 30 quality %).Utilized by this varnish gravure coater to coat after the PET film (thickness 50 μm) of supporter, 100 DEG C of dryings 10 minutes, place cooling, it is peeled off from PET film, obtains the resin substrate of FPC.The thickness of resin substrate is 30 μm.
On the two sides of the resin substrate obtained with above-mentioned step, with alligatoring face for fitting Copper Foil inner side, pressing machine is utilized to make its thermo-compressed (200 DEG C of 60min, 1MPa).The one or two sides of the Copper Foil after thermo-compressed is etched, describes wiring pattern, be made into the resin substrate of band wiring.The wiring pattern side of the resin substrate connected up at this band is configured in the mode opposed with adhesive linkage the mulch film that above-mentioned step obtains, utilize pressing machine to make its thermo-compressed and make its be heating and curing (180 DEG C, 60min, 1MPa), making printed circuit board (PCB).
Insertion loss: make to make impedance become the microstrip line (microstripline) of the patten's design of 50 Ω on above-mentioned resin substrate, attach above-mentioned adhesion film as mulch film using vacuum pressed (180 DEG C 1hr, 1MPa, vacuum tightness < 10kPa), be made into test film.The test film made is used to measure insertion loss (db) with following condition.
Measure machine: E8363B (AgilentTechnologies Inc.)
Measure frequency: 10MHz ~ 60GHz
Measuring point: 4000
Measure probe: GSG250
Cloth line length: 30mm, 50mm, 70mm
Cloth live width: 130 ± 10 μm
Result is as shown in the table.
Table 5
As shown in Table 5: the resin substrate of the band mulch film using resin combination of the present invention to make, due to insertion loss < 5db, therefore high-speed transfer is excellent.

Claims (12)

1. a resin combination, it comprises:
(A) the matter average molecular weight Mw shown in following general formula (1) is the vinyl compound of 500 ~ 4000,
[changing 1]
In formula (1), R 1, R 2, R 3, R 4, R 5, R 6and R 7can be hydrogen atom, halogen atom, alkyl, haloalkyl or phenyl identical or differently ,-(O-X-O)-represent with following structural formula (2),
[changing 2]
R 8, R 9, R 10, R 14and R 15can be halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently, R 11, R 12and R 13can be hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently,-(Y-O)-be the a kind of structure defined with following structural formula (3) or the structure become through random arrangement with the structure of more than two kinds that following structural formula (3) defines
[changing 3]
R 16and R 17can be halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently, R 18and R 19can be hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently, Z is the organic radical of carbon number more than 1 and sometimes also comprises Sauerstoffatom, nitrogen-atoms, sulphur atom, halogen atom, a and b represents the integer of 0 ~ 300 and at least any one party is not the integer that 0, c and d represents 0 or 1;
(B) styrene content is polystyrene-poly (ethylene/butylene) segmented copolymer of 15 ~ 35%;
(C) styrene content is polystyrene-poly (ethylene-vinyl/propylene) segmented copolymer of 25 ~ 40%;
(D) epoxy resin;
(E) bismaleimides; And
(F) exothermic peak utilizing means of differential scanning calorimetry and DSC to measure to obtain more than 100 DEG C and the organo-peroxide of less than 180 DEG C,
The mass ratio of each composition be (A+E)/(B+C)=more than 0.81 and less than 1.00, (B)/(C)=more than 1.00 and less than 4.00,
With the mass percent of the total mass relative to described composition (A) ~ (F), the described composition (D) containing 1 ~ 10 quality %,
With the mass percent of the content relative to described (A) composition, the described composition (F) containing 0.1 ~ 10 quality %.
2. resin combination according to claim 1, wherein,
Described composition (A)-(O-X-O)-represent with following structural formula (4), described composition (A)-structure that becomes through random arrangement of (Y-O)-have following structural formula (5) or the structure shown in following structural formula (6) or the structure shown in following structural formula (5) and the structure shown in following structural formula (6)
[changing 4]
[changing 5]
3. resin combination according to claim 1 and 2, wherein,
The organo-peroxide of described (F) composition is peroxyesters or dialkyl peroxide class.
4. the resin combination according to any one of claims 1 to 3, wherein,
The epoxy resin of described (D) composition be selected from there is not hydroxyl in the molecule biphenyl type epoxy resin, fluorenes type epoxy resin and naphthalene type epoxy resin at least a kind.
5. an adhesive film, wherein,
Comprise the resin combination according to any one of Claims 1 to 4.
6. a multilayer printed circuit board, wherein,
It employs the resin combination according to any one of Claims 1 to 4 in layers cementing.
7. a multilayer printed circuit board, wherein,
It employs adhesive film according to claim 5 in layers cementing.
8. multilayer printed circuit board according to claim 7, wherein,
The substrate forming multilayer printed circuit board for the vinyl compound shown in following general formula (1) and, rubber and/or thermoplastic elastomer be the resin substrate of principal constituent,
(A) vinyl compound shown in following general formula (1) is as follows:
[changing 4]
In formula (1), R 1, R 2, R 3, R 4, R 5, R 6and R 7can be hydrogen atom, halogen atom, alkyl, haloalkyl or phenyl identical or differently ,-(O-X-O)-represent with following structural formula (2),
[changing 5]
R 8, R 9, R 10, R 14and R 15can be halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently, R 11, R 12and R 13it can be the alkyl or phenyl of hydrogen atom, halogen atom, carbon number less than 6 identical or differently,-(Y-O)-be the a kind of structure defined with following structural formula (3) or the structure become through random arrangement with the structure of more than two kinds that following structural formula (3) defines
[changing 6]
R 16and R 17can be halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently, R 18and R 19can be hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently, Z is the organic radical of carbon number more than 1 and sometimes also comprises Sauerstoffatom, nitrogen-atoms, sulphur atom, halogen atom, a and b represents the integer of 0 ~ 300 and at least any one party is not the integer that 0, c and d represents 0 or 1.
9. a mulch film, wherein,
Comprise the resin combination according to any one of Claims 1 to 4.
10. a flexible printed circuit board, wherein,
It has mulch film according to claim 9.
11. 1 kinds of flexible printed circuit boards, is characterized in that,
In the wiring pattern side of resin substrate wiring pattern being formed at the band wiring obtained with the interarea of the resin substrate that is principal constituent of any one in liquid crystalline polymers, polyimide and PEN, use the mulch film described in claim 9.
12. 1 kinds of flexible printed circuit boards, is characterized in that,
In the wiring pattern side of resin substrate wiring pattern being formed at the band wiring obtained with the vinyl compound shown in following general formula (1) and rubber and/or the thermoplastic elastomer interarea that is the resin substrate of principal constituent, use the mulch film described in claim 9
[changing 7]
In formula (1), R 1, R 2, R 3, R 4, R 5, R 6and R 7can be hydrogen atom, halogen atom, alkyl, haloalkyl or phenyl identical or differently ,-(O-X-O)-represent with following structural formula (2),
[changing 8]
R 8, R 9, R 10, R 14and R 15can be halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently, R 11, R 12and R 13can be hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently,-(Y-O)-be the a kind of structure defined with following structural formula (3) or the structure become through random arrangement with the structure of more than two kinds that following structural formula (3) defines
[changing 9]
R 16and R 17can be halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently, R 18and R 19can be hydrogen atom, halogen atom, the alkyl of carbon number less than 6 or phenyl identical or differently, Z is the organic radical of carbon number more than 1 and sometimes also comprises Sauerstoffatom, nitrogen-atoms, sulphur atom, halogen atom, a and b represents the integer of 0 ~ 300 and at least any one party is not the integer that 0, c and d represents 0 or 1.
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